Diesel fuel oils



Patented Nov. 8, 1949 I "UNITE STAT DIESEL FUEL oiLs Herschel G. Smith, Walllngford, Troy L. Cantrell, a Lansdowne, and Mark L. Hill, Yeadon, Pa., assignors to Gulf Oil Corporation, Pittsburgh, Pa.,

a corporation of Pennsylvania No Drawing. Application May 14, 1947,

Serial No. 748,130

2 Claims. (CI. 44-71) This invention relates to improved Diesel fuel oils and more particularly to Diesel fuel oils which contain small amounts of addition agents which improve the performance characteristics of Diesel engines that burn said improved Diesel fuel oils.

Diesel engines are generally operated with fuel oils that have a boiling range above that of gasoline and below that of a motor lubricant. They may for instance have initial boiling points of about 400 F. and end boiling points of about 700 F. In the operation of Diesel engines with such petroleum fuel oils various difficulties arise. Often varnish or gum forms on the piston surfaces, cylinder walls, valves, and atomizing apparatus of Diesel engines operating on such fuel oils, and the piston rings stick. Gum formation 1 on the close fitting pintle valve of' the fuel injection equipment results in a rapid drop in power and fluctuating combustion pressure due to inconsistent fuel injection. After several days of operation on ordinary Diesel fuel oils, power output and engine efficiency decrease and there isa noticeable amount of knocking when the speed of the engine is increased. The engine must frequently be overhauled, cleaned and adjusted to restore its operating efllciency. Diesel fuel oils used in operating marine Diesel engines often become contaminated with water. As little as 0.1 per cent of water ina Diesel fuel oil. can cause corrosion of fuel injectors so serious that the injectors must necessarily be replaced.

object is to provide Diesel fuel oils which will tend to lessen the wear on the engine parts. Other objects will appear hereinafter.

These objects are accomplished in accordance "being present in sufiicient quantities to retard corrosion, wear, gum formation and ring sticking in a Diesel engine burning said Diesel fuel.

More particularly, the addition agent used in our improved Diesel fuel oils is prepared by first subjecting a sulfurized sperm oil to a partial hydrolysis, from 10 to 50, per cent by weight of the sperm oil being hydrolyzed. The product of the hydrolysis consists of a mixture of the sulfurized fatty acids of the sperm oil, the sulfurlzed fatty alcohols of the sperm oil, and unhydrolyzed sulfurized sperm oil. The entire mixture is then neutralized with a long chain primary aliphatic With certain straight-run light Pennsylvania type fuel oils the wear on the injectors and plungers is sufiicient to render them inaccurate after a few days operation thereby causing erratic engine performance. In particular, small and medium size Diesel engines'which usually operate on rather light fuel oils operate with lessened efliciency because of insuflic'ent lubrication and corrosion of parts. Corro ion, wear v and gum formation on the high pres ure injection pumps, interior cylindersurfaces and piston rings appear to be the major causes for the lessened efficiency with which Diesel engines perform when they are operated on ordinary-Diesel fuel oils.

It is an object of this invention to manufacture fuel oils for Diesel engines which will improve the power output and performance characteristics of such engines. A further object is to produce Diesel fuel oils which will deposit very little varnish or gum .on the engine parts. A still further object is to provide Diesel fuel oils which will not corrode engine parts if said oils become contaminated with water. Another amine having at least 10 carbon atoms. As may be seen, therefore, our addition agent is a mixture of aliphatic amine salts of the sulfurized sperm oil fatty acids, the sulfurized sperm oil alcohols and sulfurized sperm oil.

The sulfurized sperm oil employed in the preparation of our addition agent may be. prepared by reacting sulfur with sperm oil as set forth in U. S. Patent 2,179,066 to Herschel G. Smith. Partial hydrolysis of the sulfurized sperm oil may be accomplished in any manner known to the art, such as by heating in the presence of water and a fat splitting agent such as sulfuric acid. As has been stated, the hydrolysis is partial and from 10 per cent to per cent by weight of the sulfurized sperm oil is hydrolyzed or split into sulfurized sperm oil fatty acids and sulfurized sperm oil alcohols.

The aliphatic amine salts usedin our improved Diesel fuel oils are made from primary aliphatic amines having at least 10 carbon atoms and the mixture of fatty acids obtained by hydrolyzing sulfurized sperm oil; The normal straight chain primary aliphatic amines used in preparing the amine salts used in the present invention preferably contain from 10 to 20 carbon'atoms. Usually normal straight chain primary alkyl aminesrsuch as decyl amine, undecyl amine, dodecyl amine, tetradecyl amine, cetyl amine, octadecyl amine and eicosyl amine are employed, but it is also permissible to use unsaturated straight chain primary aliphatic amines such as undecenyl amine and 9,10-octadecenyl amine (also called oleyl amine). Mixtures of the straight chain primary alkyl amines, such as cocoamine, are often used because of their relative cheapness. Cocoamine is a commercial mixture of higher alkyl amines prepared from coconut oil fatty acids. It contains a major amount of primary doecyl amine, and typical samples thereof have been found to have average molecular weights ranging from 200 to 210.

The aliphatic amine salts used in our improved Diesel fuel oils are made by reacting approximately equimolecular proportions of amines, such as those mentioned in the preceding paragraph, with the mixture of fatty acids obtained by hydrolyzing sulfurized sperm oil. One of the amine salts which has been found to be a very desirable addition agent to Diesel fuel oils is the cocoamine salt of the mixture of fatty acids obtained by hydrolyzing sulfurized sperm oil.

The following examples further illustrate our invention:

Example I.-A sulfurized sperm oil was partially hydrolyzed to the extent of 10 per cent by weight, and the resulting partially hydrolyzed sulfurized sperm oil was neutralized with cocoamine. Ten parts by weight of the mixture of cocoamine salts of sulfurized sperm oil fatty acids, sulfurized sperm oil alcohols and unhydrolyzed sulfurized sperm oil were then blended with 90 parts by weight of a Texas oil having a viscosity of 1200 SUV at 100 F. to form a concentrate. The concentrate had the following properties:

Gravity API 22.0 Viscosity, SUV:

100 F 1490 210 F 86 Flash, F 460 Fire, 00 F 510 Pour F +5 Example II.A sulfurized sperm oil was partially hydrolyzed to the extent of 50 per cent by weight, and the resulting partially hydrolyzed sulfurized sperm oil was neutralized with cocoamine. Ten parts by weight of the resulting mixture were then blended with 90 parts by weight of a Texas oil having a viscosity of 1200 SUV at 100 F. to form a concentrate. The concentrate had the following properties:

Gravity API.. 21.8

Viscosity, SUV:

Flash, 00 F 465 ire, 0C F 515 Pour- F +15 fuel oil. Preferably 0.5 per cent by volume of the above concentrate, or 0.05 per cent by weight of the addition agent per se is employed. If desired we may dispense entirely with the formation of concentrates and add our addition agent directly to the Diesel fuel oil in the desired proportions.

Example III.-An improved light Diesel fuel was prepared by blending 0.5 per cent by volume of the concentrate prepared according to Example I and 99.5 per cent by volume of Diesel fuel oil. A comparison ofthe properties of the improved and unimproved fuel oils is as follows:

Diesel Improved Fuel Diesel Base Oil Fuel Oil Gravity, API 42. 5 42. B Viscosity, SUV, 100 F 31 31 F P-M, F 146 146 Pour, F 60 -40 Sulfur, L, per cent O. 05 0. 08 Carbon Residue, per cent trace trace Carbon Residue on 10% Bottoms, per cent trace trace Cggosion Test No. l oi Patent No. 2, 371,-

Steel Strip Appearance" rust bri ht Area Rusted, per cent... 100 nll Neutralization No. nil nll Acid Heat, F., ASTM D48l-39 nil nil Aniline Point, F., ASTM D6ll-44'I, 145 145 Diesel Index No 61. 7 61. 7 Cetane No., ASTM D6l3-43T 63 (i3 Distillation, Gas Oil, ASTM B15841:

Over Point F 347 347 End Point, F 624 630 kg? at F. 386 386 at F- 429 432 0 at F 488 404 Example IV.-A heavy Diesel fuel oil was prepared by blending 0.5 per cent by volume of the concentrate prepared according to Example II with 99.5 per cent by volume of a heavy Diesel fuel oil. A comparison by the properties of the improved and unimproved fuel oils is as follows:

Base Improved Oil Oil Gravity, API 24. 5 24. 4 Viscosity SUV:

210 F 44 44 Flash, P-M, F., ASTM 1193-46.. 250 250 Pour, F- +40 +35 Sulfur, L, per cent 0. 40 0.45 Water and Sediment, per cent 0.10 0. l0 Sediment, per cent, ASTM D473-38T. 0.01 0.01 Carbon Residue, per cent 1.50 1.50 Precipitation No.. trace trace Ash per cent 0.01 0.01 BTU/Lb., Gross 19, 188 19,188 Cgrggjsigfna Test No. l of U. S. Patent No. rust bright Corrosion Test, ASTM D665-44 T:

Steel Strip Appearance rust bright Area Rusted, per cent 100 The Diesel fuel oils of the present invention such as those described in the preceding examples display many advantages over ordinary Diesel fuel oils. The close fitting pintle valves in the injection equipment of Diesel engines burning our improved fuel oils do not become covered with gum or corroded, and therefcre the combustion pressure and power output remain constant even after more than 1000 hours of operation. This is an important advantage especially in connection with the operation of marine Diesel engines such as those used in power barges. Our new Diesel fuel oils substantially prevent corrosion and wear of the high pressure injection pumps, interior cylinder surfaces and piston rings, and reduce the tendency for piston rings to stick. Our Diesel fuels thus improve markedly 75 the performance of Diesel engines, particularly those of small and medium size that usually operate on ratherlight fuel oils. The Diesel oils of the present invention decrease the tendency toous corrosion of the injectors will ensue, sincethe addition agents added to our fuel oils increase water tolerance. The wear on the plungers and injectors decreases considerably when our fuel oils are employed. Our improved Diesel fuel oils successfully counteract many of the factors that decrease the efficiency of Diesel engines operating on ordinary Diesel fuels.

We claim:

1. An improved Diesel fuel oil which consists of Diesel fuel oil and from about 0.01 per cent to about 1.0 per cent by weight of the products obtained by neutralizing with a long chain primary 26 6 aliphatic amine having at least 10 carbon atoms the mixture of fatty acids, alcohols and sulfurized sperm oil obtained by partially hydrolyzing, from 10 to 50 per cent by weight, a sulfurized sperm oil. 2. An improved Diesel fuel oil which consists of Diesel fuel oil and about 0.05 per cent by weight of the products obtained by neutralizing with cocoamine the mixture of fatty acids, alcohols and sulfurized sperm oil obtained by partially hydrolyzing, from 10 to 50 per cent by weight, a sulfurized sperm oil.

HERSCHEL G. SMITH.

TROY L. CANTRELL.

MARK L. HILL.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,179,066 Smith Nov. 7, 1939 2,330,524 Shields Sept. 28, 1943 2,344,016 Anderson Mar. 14, 1944 2,401,993 Wasson June 11, 1946 

